The present invention relates to oxime ethers of the general formula 
in which R1 is C1-4alkyl, (Yxe2x80x94X) is CH2xe2x95x90, C1-2alkylthio-CHxe2x95x90 or C1-2alkyl-ONxe2x95x90 and Z is an aldimino or ketimino group, namely in particular a group 
in which R2 is hydrogen, C1-4alkyl, C1-4haloalkyl, C3-6cycloalkyl, C2-4alkenyl, C2-4alkynyl, C1-2alkoxymethyl, C1-2alkylthiomethyl, C1-4alkylsulfonyl, C1-3alkoxy, C1-3alkylthio or cyano, and R3 is C1-6alkyl, aryl-C1-4alkyl, heteroaryl-C1-4alkyl, C2-12alkenyl, aryl-C2-4alkenyl, aryloxy-C1-4alkyl, heteroaryloxy-C1-4alkyl, heteroaryl-C2-4alkenyl, C3-6cycloalkyl, aryl, heteroaryl, C2-5alkanoyl, aroyl or heteroaroyl, or R2 and R3 together with the carbon atom to which they are bonded form a substituted or unsubstituted four- to seven-membered saturated or unsaturated ring which may contain an oxygen atom, sulfur atom and/or nitrogen atom and which can additionally have a substituted or unsubstituted fused benzene ring.
The compounds according to the invention have fungicidal properties and are suitable as fungicidal active compounds, in particular for use in agriculture and horticulture.
The invention furthermore relates to a process for the preparation of the compounds according to the invention, to fungicidal compositions comprising such compounds as active substances, and to the use of such compounds and compositions for controlling fungi in agriculture and in horticulture.
In a narrower sense, the present invention relates to oxime ethers of the formula I in which R1 is C1-4alkyl, (Yxe2x80x94X) is CH2xe2x95x90, C1-2alkylthio-CHxe2x95x90 or C1-2alkyl-ONxe2x95x90 and Z is an aldimino or ketimino group, namely in particular a group 
in which R2 is hydrogen, C1-4alkyl, C1-4haloalkyl or C3-6cycloalkyl and R3 is C1-6alkyl, aryl-C1-4alkyl, heteroaryl-C1-4alkyl, C2-6alkenyl, aryl-C2-4alkenyl, heteroaryl-C2-4alkenyl, C3-6cycloalkyl, aryl, heteroaryl, C2-5alkanoyl, aroyl or heteroaroyl, or R2 and R3 together with the carbon atom to which they are bonded form a substituted or unsubstituted four- to seven-membered saturated ring which may contain an oxygen or sulfur atom and which can additionally have a substituted or unsubstituted fused benzene ring.
In the above formula I and in the following text, all groups xe2x80x9calkylxe2x80x9d and xe2x80x9calkenylxe2x80x9d, as such or as part of larger groups, for example heteroarylalkyl, can be straight-chain or branched, depending on the number of carbon atoms. Moreover, the alkenyl groups can have one or more double bonds. Halogen as a substituent is fluorine, chlorine, bromine or iodine, fluorine, chlorine and bromine being preferred A haloalkyl group can have one or more identical or different halogen substituents. Aryl is understood as meaning, in particular, phenyl, naphthyl, phenanthryl or fluorenyl. Heteroaryl is a heterocyclic group having aromatic character and 1-3 hetero atoms N, O and/or S. Preferred rings are triazole or other five-membered and six-membered rings having 1-2 hetero atoms which, in turn, can additionally have one or two fused benzene rings.
Examples which may mentioned and which do not represent any limitation but which, for the sake of simplicity, are referred to as xe2x80x9cHet* groupxe2x80x9d in the following text, are pyrrolyl, pyridyl, furyl, thienyl, isoxazolyl, thiazolyl, pyrazinyl, pyridazinyl, imidazolyl, pyrimidinyl or triazolyl, or such a group with fused benzene, for example quinolinyl, quinoxalinyl, benzofuryl, benzothienyl or dibenzofuryl. This also applies analogously to xe2x80x9carylxe2x80x9d or xe2x80x9cheteroarylxe2x80x9d as part of a larger group, for example aralkyl or heteroarylalkyl. Each of the aryl and heteroaryl groups can have one or more of the following substituents: halogen, C1-4alkyl, C1-4haloalkyl, aryl-C1-4alkyl, aryloxy-C1-4alkyl, C2-4alkenyl, aryl-C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl, aryl, C1-4alkoxy, C1-4haloalkoxy, aryl-C1-4alkoxy, C1-4alkylthio, aryloxy, cyano, nitro, C2-4haloalkenyl, C2-4haloalkynyl, C2-4alkenyloxy, C2-4haloalkenyloxy, C3-4alkynyloxy, C3-4haloalkynyloxy, cyclopropylmethoxy, cyclopropyl (unsubstituted or mono- to trisubstituted by halogen and/or methyl), cyanomethoxy (xe2x80x94OCH2CN), C1-4alkoxymethyl, C1-4alkylthiomethyl, C1-4alkylsulfinylmethyl, C1-4alkylsulfonylnethyl, arylthio, thiocyanato, C1-4alkoxyiminomethyl, C1-4alkanoyloxy and C1-4alkoxycarbonyl; and also a heteroaryl radical, a heteroaryl-C1-4alkyl radical, a heteroaryloxy-C1-4alkyl radical, a heteroaryl-C2-4alkenyl radical, a heteroaryl-C1-4alkoxy radical or a heteroaryloxy radical; the term heteroaryl being understood as meaning a representative of the abovementioned xe2x80x9cHet* groupxe2x80x9d.
Almost all of the abovementioned substituents for aryl and heteroaryl groups can occur once to twice, preferably once, with the exception of C1-4alkyl, which is suitable as a substituent up to four times and halogen, which can occur up to three times, and, in the case of fluorine, also up to five times.
The preferred aryl radical is phenyl, whether on its own or as part of another substituent. Accordingly, benzoyl is preferred as aroyl.
C2Alkanoyl is acetyl. Haloalkyl is understood as meaning alkyl groups which are up to hexasubstituted by identical or different substituents from the series comprising F, Cl, Br and/or I. Examples of haloalkyl groups, on their own or as part of another substituent (such as haloalkoxy) are CH2Cl, CHCl2, CCl3, CHBr2, CH2CH2Cl, CHClxe2x80x94CHCl2, CF2Cl, CH2I, CF3, C2F5, CF2xe2x80x94CF2Cl, CHF2, CH2F, CF2CHFCF3.
Trifluoromethyl, difluoromethoxy and trifluoromethoxy are preferred.
Moreover, the aryl groups (in particular phenyl) can carry a five-, six- or seven-membered saturated or unsaturated ring which has one or two oxygen atoms and which can be unsubstituted or mono- or polysubstituted by methyl, methoxy, phenyl, halogen, cyano or oxo (Cxe2x95x90O). Examples of such groups are 5-benzofuryl, 6benzodioxanyl and 5-(1 ,3-benzodioxolyl).
In the event that R2 and R3 together with the carbon atom to which they are bonded form a substituted or unsubstituted ring as has been described in greater detail above, suitable substituents of the ring 
are, in particular, C1-6alkyl or substituted or unsubstituted phenyl. It is also possible for the fused benzene ring which may be present to be substituted. Possible substituents of the phenyl group, or of the benzene ring itself, are those mentioned above in connection with the aryl group.
If asymmetric carbon atoms are present in the compounds of the formula I, the compounds exist in optically active form. Merely because of the presence of the aliphatic or imino double bond Xxe2x95x90C and the imino double bond of the aldimino or ketimino group Z, the compounds exist in any case in the [E] or [Z] form. Atropisomerism can also occur. The formula I is intended to embrace all these isomeric forms which are possible as well as their mixtures, for example racemic mixtures and any desired [E/Z] mixtures.
In the case of the compounds of the formula I R1 is preferably methyl; and, independently thereof, (Yxe2x80x94X) is preferably methylene, methylthiomethylene (CHxe2x80x94SCH3) or methoxyimino (Nxe2x80x94OCH3); compounds in which R1 is methoxyimino are particularly preferred.
In the group (R2)(R3)Cxe2x95x90Nxe2x80x94, R2 is preferably hydrogen, C1-4alkyl (in particular methyl or ethyl), C1-4haloalkyl (in particular trifluoromethyl) or C3-6cycloalkyl (in particular cyclopropyl), and R3 is preferably substituted or unsubstituted phenyl, naphthyl (in particular xcex2-naphthyl) or benzyl, possible substituents preferably being up to three identical or different halogen atoms (in particular fluorine, chlorine and/or bromine), C1-4aLkyl groups (in particular methyl), C1-4haloalkyl groups (in particular trifluoromethyl), C1-4haloalkoxy groups (in particular trifluoromethoxy) and alkylenedioxy (in particular 3,4methylenedioxy), or heteroaryl, in particular furyl which is unsubstituted or substituted by up to two methyl groups, or thienyl, pyridyl or benzofuryl which is unsubstituted or substituted by chlorine or methyl.
In the event that R3 is heteroaryl, R2 is preferably methyl.
Other representatives of compounds of the formula I are:
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94Z) is CH2, Z is a group (R2)(R3)Cxe2x95x90Nxe2x80x94, R2 is methyl and R3 is 3-trifluoromethylbenzyl, 4-chloro-3-trifluoromethylbenzyl, 1,4,8-trimethylnona-1,3,7-trienyl, phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-fluoro-5-methylphenyl, 4-methoxyphenyl, 3,4,5-trimethoxyphenyl, 3-trifluoromethoxyphenyl, 3,5-di(trifluoromethyl)phenyl, xcex2-naphthyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-benzofuryl or 5-chloro-2-thienyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is CH2, Z is a group (R2)(R3)Cxe2x95x90Nxe2x80x94, R3 is phenyl and R2 is ethyl, propyl or isopropyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is CH2, Z is a group (R2)(R3)Cxe2x95x90Nxe2x80x94, R2 is trifluoromethyl and R3 is 2-(xcex2-naphthyl)ethenyl, phenyl, 3-chlorophenyl, 4-chlorophenyl, p-tolyl, xcex1,xcex1,xcex1-trifluoro-m-tolyl, xcex2-naphthyl or 2-pyridyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is CH2, Z is a group (R2)(R3)Cxe2x95x90Nxe2x80x94, R2 is cyclopropyl and R3 is phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, xcex1,xcex1,xcex1-trifluoro-m-tolyl, 4-phenoxyphenyl or xcex2-naphthyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is methylthiomethylene, (xe2x95x90CHxe2x80x94SCH3), Z is a group (R2)(R3)Cxe2x95x90Nxe2x80x94, R2 is methyl and R3 is 3-trifluoromethylbenzyl, 4-chloro3-trifluoromethylbenzyl, 1,4,8-trimethylnona-1,3,7-trienyl, phenyl, 4-fluoro-phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, 3,5-dichlorophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-fluoro-5-methylphenyl, 4-methoxyphenyl, 3,4,5-trimethoxyphenyl, 3-trifluoromethoxyphenyl, 3,5-di(trifluoromethyl)phenyl, 2-furyl, 2-benzofuryl or 5-chloro-2-thienyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is methylthiomethylene, Z is a group (R2)(R3)Cxe2x95x90Nxe2x80x94, R2 is trifluoromethyl and R3 is 2-(xcex2-naphthyl)ethenyl, phenyl, 3-chlorophenyl, 4-chlorophenyl, p-tolyl, xcex1,xcex1,xcex1-trifluoro-m-tolyl, xcex2-naphthyl or 2-pyridyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is methylthiomethylene, Z is a group R2R3Cxe2x95x90Nxe2x80x94, R2 is cyclopropyl and R3 is phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, xcex1,xcex1,xcex1-trifluoro-m-tolyl, 4-phenoxyphenyl or xcex2-naphthyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is methoxyimino (xe2x95x90Nxe2x80x94OCH3), Z is a group (R2)(R3)Cxe2x95x90Nxe2x80x94, R2 is methyl and R3 is 4-chloro-3-trifluoromethylbenzyl, phenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2-fluoro-5-methylphenyl, 3-trifluoromethoxyphenyl or 5-chloro2-thienyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is methoxyimino, Z is a group R2R3Cxe2x95x90Nxe2x80x94, R2 is trifluoromethyl and R3 is 2-(xcex2-naphthyl)ethenyl, phenyl, 3-chloro-phenyl, 4-chlorophenyl, p-tolyl, xcex1,xcex1,xcex1-trifluoro-m-tolyl, xcex2-naphthyl or 2-pyridyl;
those compounds of the formula I in which R1 is methyl, (Yxe2x80x94X) is methoxyimino, Z is a group R2R3Cxe2x95x90Nxe2x80x94, R2 is cyclopropyl and R3 is 3-chlorophenyl, 4-chlorophenyl, 3-bromo-phenyl, xcex1,xcex1,xcex1-trifluoro-m-tolyl, 4-phenoxyphenyl or xcex2-naphthyl;
The process according to the invention for the preparation of the compounds of the formula I comprises reacting an oxime Zxe2x80x94OH, in particular an oxime of the general formula 
in which R2 and R3 are as defined above, with a benzyl alcohol derivative of the general formula 
in which R1 and Yxe2x80x94X are as defined above and U is a leaving group.
This reaction is a nucleophilic substitution, which can be carried out under the reaction conditions which are customary for this type of reaction. The leaving group U in the benzyl alcohol derivative of the formula III is preferably understood as meaning chlorine, bromine, iodine, mesyloxy, benzenesulfonyloxy or tosyloxy. The reaction is expediently carried out in an inert organic diluent such as a cyclic ether, for example tetrahydrofuran or dioxane, acetone, dimethylfornamide or dimethyl sulfoxide, in the presence of a base such as sodium hydride, sodium carbonate or potassium carbonate, or a tertiary amine, for example a trialkylamine, in particular diazabicyclononane or diazabicycloundecane, or silver oxide, at temperatures between xe2x88x9220xc2x0 C. and 80xc2x0 C., preferably in a temperature range of from 0xc2x0 C. to 20xc2x0 C.
Alternatively, the reaction can be effected in an organic solvent, for example methylene chloride, with phase-transfer catalysis, in the presence of an aqueous basic solution, for example sodium hydroxide solution, and in the presence of a phase-transfer catalyst, for example tetrabutylammonium hydrogen sulfate, at room temperature [see, for example, W. E. Keller, xe2x80x9cPhasen-Transfer Reactionsxe2x80x9d [Phase-Transfer Reactions], Fluka-Compendium Vol. I and II, George Thieme Verlag, Stuttgart (1986/1987), in which particular mention is made of Chemistry Letters 1980, pages 869-870].
The compounds of the formula I which have been prepared in this manner can be isolated and purified by methods known per se. Equally, any mixtures of isomers which may have been obtained, for example mixtures of E/Z isomers, can be separated to give the pure isomers, for example by chromatography or fractional crystallisation.
The oximes Zxe2x80x94OH, for example those of the formula II, which are used as starting materials in the process according to the invention are either known or can be prepared by methods known per se, for example by reacting the corresponding carbonyl compound R2R3Cxe2x95x90O with hydroxylamine chloride in the presence of a base, for example sodium hydroxide or potassium hydroxide or pyridine. More methods can be found in Houben-Weyl, xe2x80x9cMethoden der Organischen Chemiexe2x80x9d [Methods of Organic Chemistry], Volume X/4, pages 3-308 (1968) xe2x80x9cHerstellung und Umwandlung von Oximenxe2x80x9d [Preparation and Conversion of Oximes].
Equally, the starting materials of the formula III, i.e. the alkyl xcex1-(2-UCH2-phenyl)-acrylates of the formula IIIa, the alkyl xcex1-(2-UCH2-phenyl)-xcex2-(C1-2alkylthio)acrylates of the formula IIIb and the alkyl 2-(2-UCH2-phenyl)glyoxylate Oxe2x80x94(C1-2alkyl)oxime of the formula IIIc 
are either known or can be prepared by methods known per se. For example, European Patent Publication (EP) 348 766 describes the preparation of methyl xcex1-(2-bromomethylphenyl)acrylate, EP 310 954 and Angew. Chem. 71, 349-365 (1959) describe the preparation of methyl xcex1-(2-bromomethylphenyl)-xcex2-methylthioacrylate, and EP 363 818 and also Angew. Chem. 71, 349-365 (1959) describe the preparation of methyl 2-(2-bromomethylphenyl)glyoxylate O-methyloxime. The compounds of the formulae IIIa, IIIb and IIIc, which are novel to date, form a further subject of the present invention.
To prepare a C1-4alkyl xcex1-(2-bromomethylphenyl)-xcex2-methylthioacrylate, a synthesis which differs from the process described in EP 310 954 can also be used, which embraces, as the first step, the bromination of the corresponding C1-4alkyl 3(4bromobenzenesulfonyloxy)-2-(o-tolyl)acrylate with N-bromosuccinimide to give the C1-4alkyl 3-(4-bromobenzenesulfonyloxy)-2-(2-bromomethylphenyl)acrylate and, as the second step, the reaction of the last-mentioned ester with sodium methanethiolate to give the desired end product. The starting material methyl 3-(4bromobenzenesulfonyloxy)-2-(o-tolyl)acrylate is described, for example, in EP 310 954.
The compounds according to the invention have a fungicidal action and can accordingly be used for controlling, or preventing, fungal attack in agriculture, in horticulture and in the protection of wood. They are particularly suitable for inhibiting the growth of or for destroying phytopathogenic fungi on parts of plants, for example leaves, stalks, roots, tubors, fruit or flowers, and on seed, as well as for destroying harmful soil fungi. Furthermore, wood-destroying and wood-discolouring fungi can be controlled using the compounds according to the invention. The compounds according to the invention are effective, for example, in the control of fungi of the classes of the Deuteromycetes, Ascomycetes, Basidiomycetes and phycomycetes.
The compounds according to the invention are particularly suitable for controlling the following pathogens:
Powdery mildews (for example Erysiphe graminis, Erysiphe cichoracearum, Podosphaera leucotricha, Uncinula necator, Sphaerotheca spp.)
Rusts (for example Puccinia tritici, Puccinia recondita, Puccinia hordei, Puccinia coronata, Puccinia striiformis, Puccinia arachidis, Hemileia vastatrix, Uromyces fabae)
Scabs (for example Venturia inaequalis)
Cercospora spp. (for example Cercospora arachidicola, Cercospora beticola)
Mycosphaerella spp. (for example Mycosphaerella fijiensis)
Alternaria spp. (for example Alternaria brassicae, Alternaria mali)
Septoria spp. (for example Septoria nodorum)
Helminthosporium spp. (for example Helminthosporium teres, Helminthosporium oryzea)
Plasmopara spp. (for example Plasmopara viticola)
Pseudoperonospora spp. (for example Pseudoperonospora cubensis)
Phytophthora spp. (for example Phytophthora infestans)
Pseudocercosporella spp. (for example Pseudocercosporella herpotrichoides)
Piricularia spp. (for example Piricularia oryzae)
Furthermore, the compounds act for example against fungi of the genera Tilletia, Ustilago, Rhizoctonia, Verticillium, Fusarium, Pythium, Gaeumannomyces, Sclerotinia, Monilia, Botrytis, Peronospora, Bremia, Gloeosporium, Cercosporidium, Penicillium, Ceratocystis, Rhynchosporium, Pyrenophora, Diaporthe, Ramularia and Leptosphaeria. Moreover, certain representatives of the compounds according to the invention have an action against fungi which damage wood, for example those of the genera Coniophora, Gloeophyllum, Poria, Merulius, Trametes, Aureobasidium, Sclerophoma and Trichoderma.
The compounds of the formula I according to the invention are distinguished by a prophylactic and curative, but mainly by a noticeable systemic action.
Under greenhouse conditions, they act against phytopathogenic fungi at concentrations of from as little as 0.5 mg to 500 mg of active substance per litre of spray mixture. In the field, it is advantageous to apply dosage rates of from 20 g to 1 kg of active substance of the formula I per hectare per treatment. To control seed-borne or soil-borne fungi by the seed-dressing method, it is advantageous to use dosage rates of from 0.001 g to 1.0 g of active substance of the formula I per kg of seed.
The compounds according to the invention can be formulated to give various compositions, for example solutions, suspensions, emulsions, emulsifiable concentrates and preparations in the form of powders. The fungicidal compositions according to the invention comprise an effective amount of at least one compound of the general formula I, as defined above, as well as formulation auxiliaries. The compositions advantageously comprise at least one of the following formulation auxiliaries:
solid carriers; solvents or dispersants; surfactants (wetting agents and emulsifiers); dispersants (without surfactant action); and stabilisers.
As solid carriers, the following are mainly suitable: natural mineral substances, such as kaolin, clays, kieselguhr, talc, bentonite, chalk, for example whiting, magnesium carbonate, limestone, quartz, dolomite, attapulgite, montmorillonite and diatomaceous earth; synthetic mineral substances, such as highly-isperse silica, aluminium oxide and silicates; organic substances, such as cellulose, starch, urea and synthetic resins; and fertilisers, such as phosphates and nitrates, it being possible for such carriers to be, for example, in the form of granules or powders.
As solvents or dispersants, the following are mainly suitable: aromatics, such as toluene, xylenes, benzene and alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons, such as cyclohexane and paraffins, for example mineral oil fractions; alcohols, such as butanol and glycol, as well as their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and strongly polar solvents and dispersants such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, such solvents and dispersants preferably having flash points of at least 30xc2x0 C. and boiling points of at least 50xc2x0 C., and water. Amongst the solvents or dispersants, so-called liquefied gaseous extenders or carriers, which are products which are gaseous at room temperature and under atmospheric pressure, are also suitable. Examples of such products are, in particular, aerosol propellants, such as (halo)hydrocarbons. In the event that water is used as solvent, it is also possible for, for example, organic solvents to be used as auxiliary solvents.
The surfactants (wetting agents and emulsifiers) can be nonionic compounds, such as condensation products of fatty acids, fatty alcohols or fatty-substituted phenols with ethylene oxide; fatty acid esters and fatty acid ethers of sugars or polyhydric alcohols; the products obtained from sugars or polyhydric alcohols by condensation with ethylene oxide; block copolymers of ethylene oxide with propylene oxide; or alkyldimethylamine oxides.
The surfactants can also represent anionic compounds, such as soaps; fatty sulfate esters, for example dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate; alkylsulfonates, arylsulfonates and fatty-aromatic sulfonates, such as alkylbenzenesulfonates, for example calcium dodecylbenzenesulfonate, and butylnaphthalenesulfonate; and more complex fatty sulfonates, for example the amide condensation products of oleic acid and N-methyltaurine, and the sodium sulfonate of dioctyl succinate.
Finally, the surfactants can be cationic compounds, such as alkyldimethyl-benzylammonium chlorides, dialkyldimethylammonium chlorides, alkyltrimethylammonium chlorides and ethoxylated quaternary ammonium chlorides.
As dispersants (without surfactant action) the following are mainly suitable: lignin, sodium salts and ammonium salts of ligninsulfonic acid, sodium salts of maleic anhydrideldiisobutylene copolymers, sodium salts and ammonium salts of sulfonated polycondensation products of naphthalene and formaldehyde, and sulfite waste liquors.
Examples of dispersants which can be employed and are particularly suitable as thickeners or anti-settling agents are methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.
Examples of suitable stabilisers are acid-binding agents, for example epichlorohydrin, phenyl glycidyl ether and soya epoxides; antioxidants, for example gallic esters and butylhydroxytoluene; UV absorbers, for example substituted benzophenones, diphenylacrylonitrile acid esters and cinnanic esters; and deactivators, for example salts of ethylenediaminetetraacetic acid, and polyglycols.
Besides the active compounds of the formula I, the fungicidal compositions according to the invention can also comprise other active compounds, for example other types of fungicidal compositions, insecticidal and acaricidal compositions, bactericides, plant growth regulators and fertilisers. Such combination compositions are suitable for broadening the spectrum of action or for specifically influencing plant growth.
In general, the compositions according to the invention comprise between 0.0001 and 85 per cent by weight of a compound or compounds according to the invention as active substance(s), depending on the nature of these compositions. They can be in a form which is suitable for storage and transport In such forms, for example emulsifiable concentrates, the concentration of active substance is usually in the higher range of the above concentration interval. These forms can then be diluted with identical or different formulation auxiliaries to concentrations of active substance which are suitable for use in practice, and such concentrations are usually in the lower range of the above concentration interval. Emulsifiable concentrates generally comprise 5 to 85 per cent by weight, preferably 25 to 75 per cent by weight, of the compound(s) according to the invention. Suitable as use forms are, inter alia, ready-for-use solutions, emulsions and suspensions, which are suitable, for example, as spray mixtures. The concentrations in such spray mixtures can be, for example, between 0.0001 and 20 per cent by weight. In the ultra-low volume method, it is possible to formulate spray mixtures in which the concentration of active substance is preferably from 0.5 to 20 per cent by weight, while the concentration of active substance in the spray mixtures formulated in the low-volume method and in the high-volume method is preferably from 0.02 to 1.0, or 0.002 to 0.1, per cent by weight.
The fungicidal compositions according to the invention can be prepared by mixing at least one compound according to the invention with formulation auxiliaries.
The compositions can be prepared in a known manner, for example by mixing the active substances with solid carriers, by dissolving or suspending them in suitable solvents or dispersants, if appropriate with the use of surfactants as wetting agents or emulsifiers, or of dispersants, by diluting pre-prepared emulsifiable concentrates with solvents or dispersants, etc.
In the case of compositions in the form of powders, the active substance can be mixed with a solid carrier, for example by concomitant grinding; or the solid carrier can be impregnated with a solution or suspension of the active substance, and the solvent or dispersant can then be removed by evaporation, heating or by filtering off with suction under reduced pressure. By adding surfactants or dispersants, it is possible to make such compositions in the form of powders readily wettable with water, so that they can be converted into aqueous suspensions which are suitable, for example, as spray liquors.
Alternatively, the compounds according to the invention can be mixed with a surfactant and a solid carrier to form a wettable powder which is dispersible in water, or they can be mixed with a solid pregranulated carrier to form a product in the form of granules.
If desired, a compound according to the invention can be dissolved in a solvent which is not miscible with water, for example an alicyclic ketone, which advantageously contains dissolved emulsifier, so that the solution is self-emulsifying when added to water. On the other hand, the active substance can be mixed with an emulsifier, and the mixture can then be diluted with water to the desired concentration. Moreover, the active substance can be dissolved in a solvent and the solution can then be mixed with an emulsifier. Such a mixture can equally be diluted with water to the desired concentration. In this manner, emulsifiable concentrates, or ready-for-use emulsions, are obtained
The compositions according to the invention can be used by the application methods customary in crop protection or in agriculture. The process according to the invention for controlling fungi comprises treating the locus to be protected or the goods to be protected, for example plants, parts of plants, or seeds, with an effective amount of a compound according to the invention, or a composition according to the invention.